NO 2 converts to the colorless dinitrogen tetroxide (N 2O 4) at low temperatures and reverts to NO 2 at higher temperatures. | |||
Names | |||
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IUPAC name Nitrogen dioxide | |||
Other names Nitrogen(IV) oxide, [1] deutoxide of nitrogen | |||
Identifiers | |||
3D model (JSmol) | |||
ChEBI | |||
ChemSpider | |||
ECHA InfoCard | 100.030.234 | ||
EC Number |
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976 | |||
PubChem CID | |||
RTECS number |
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UNII | |||
UN number | 1067 | ||
CompTox Dashboard (EPA) | |||
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Properties | |||
NO• 2 | |||
Molar mass | 46.005 g·mol−1 | ||
Appearance | Brown gas [2] | ||
Odor | Chlorine-like | ||
Density | 1.880 g/L [2] | ||
Melting point | −9.3 °C (15.3 °F; 263.8 K) [2] | ||
Boiling point | 21.15 °C (70.07 °F; 294.30 K) [2] | ||
Hydrolyses | |||
Solubility | Soluble in CCl 4, nitric acid, [3] chloroform | ||
Vapor pressure | 98.80 kPa (at 20 °C) | ||
+150.0·10−6 cm3/mol [4] | |||
Refractive index (nD) | 1.449 (at 20 °C) | ||
Structure | |||
C2v | |||
Bent | |||
Thermochemistry [5] | |||
Heat capacity (C) | 37.2 J/(mol·K) | ||
Std molar entropy (S⦵298) | 240.1 J/(mol·K) | ||
Std enthalpy of formation (ΔfH⦵298) | +33.2 kJ/mol | ||
Hazards | |||
Occupational safety and health (OHS/OSH): | |||
Main hazards | Poison, oxidizer | ||
GHS labelling: | |||
Danger | |||
H270, H314, H330 | |||
P220, P260, P280, P284, P305+P351+P338, P310 | |||
NFPA 704 (fire diamond) | |||
Lethal dose or concentration (LD, LC): | |||
LC50 (median concentration) | 30 ppm (guinea pig, 1 h) 315 ppm (rabbit, 15 min) 68 ppm (rat, 4 h) 138 ppm (rat, 30 min) 1000 ppm (mouse, 10 min) [6] | ||
LCLo (lowest published) | 64 ppm (dog, 8 h) 64 ppm (monkey, 8 h) [6] | ||
NIOSH (US health exposure limits): | |||
PEL (Permissible) | C 5 ppm (9 mg/m3) [7] | ||
REL (Recommended) | ST 1 ppm (1.8 mg/m3) [7] | ||
IDLH (Immediate danger) | 13 ppm [7] | ||
Safety data sheet (SDS) | ICSC 0930 | ||
Related compounds | |||
Related nitrogen oxides | Dinitrogen pentoxide Dinitrogen tetroxide Contents | ||
Related compounds | Chlorine dioxide Carbon dioxide | ||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). |
Nitrogen dioxide is a chemical compound with the formula NO2. One of several nitrogen oxides, nitrogen dioxide is a reddish-brown gas. It is a paramagnetic, bent molecule with C2v point group symmetry. Industrially, NO2 is an intermediate in the synthesis of nitric acid, millions of tons of which are produced each year, primarily for the production of fertilizers.
Nitrogen dioxide is poisonous and can be fatal if inhaled in large quantities. [8] The LC50 (median lethal dose) for humans has been estimated to be 174 ppm for a 1-hour exposure. [9] It is also included in the NOx family of atmospheric pollutants.
Nitrogen dioxide is a reddish-brown gas with a pungent, acrid odor above 21.2 °C (70.2 °F; 294.3 K) and becomes a yellowish-brown liquid below 21.2 °C (70.2 °F; 294.3 K). It forms an equilibrium with its dimer, dinitrogen tetroxide (N2O4), and converts almost entirely to N2O4 below −11.2 °C (11.8 °F; 261.9 K). [7]
The bond length between the nitrogen atom and the oxygen atom is 119.7 pm. This bond length is consistent with a bond order between one and two.
Unlike ozone (O3) the ground electronic state of nitrogen dioxide is a doublet state, since nitrogen has one unpaired electron, [10] which decreases the alpha effect compared with nitrite and creates a weak bonding interaction with the oxygen lone pairs. The lone electron in NO2 also means that this compound is a free radical, so the formula for nitrogen dioxide is often written as •NO2.
The reddish-brown color is a consequence of preferential absorption of light in the blue region of the spectrum (400–500 nm), although the absorption extends throughout the visible (at shorter wavelengths) and into the infrared (at longer wavelengths). Absorption of light at wavelengths shorter than about 400 nm results in photolysis (to form NO + O, atomic oxygen); in the atmosphere the addition of the oxygen atom so formed to O2 results in ozone.
This section needs additional citations for verification .(January 2023) |
Nitrogen dioxide typically arises via the oxidation of nitric oxide by oxygen in air (e.g. as result of corona discharge): [11]
Nitrogen dioxide is formed in most combustion processes using air as the oxidant. At elevated temperatures nitrogen combines with oxygen to form nitrogen dioxide:
In the laboratory, NO
2 can be prepared in a two-step procedure where dehydration of nitric acid produces dinitrogen pentoxide:
which subsequently undergoes thermal decomposition:
The thermal decomposition of some metal nitrates also generates NO2:
NO2 is generated by the reduction of concentrated nitric acid with a metal (such as copper):
Nitric acid decomposes slowly to nitrogen dioxide by the overall reaction:
The nitrogen dioxide so formed confers the characteristic yellow color often exhibited by this acid.
NO2 exists in equilibrium with the colourless gas dinitrogen tetroxide (N2O4):
The equilibrium is characterized by ΔH = −57.23 kJ/mol, which is exothermic. NO2 is favored at higher temperatures, while at lower temperatures, N2O4 predominates. N2O4 can be obtained as a white solid with melting point −11.2 °C. [11] NO2 is paramagnetic due to its unpaired electron, while N2O4 is diamagnetic.
At 150 °C (302 °F; 423 K), NO2 decomposes with release of oxygen via an endothermic process (ΔH = 14 kJ/mol):
As suggested by the weakness of the N–O bond, NO2 is a good oxidizer. Consequently, it will combust, sometimes explosively, in the presence of hydrocarbons. [12]
NO2 reacts with water to give nitric acid and nitrous acid:
This reaction is one of the steps in the Ostwald process for the industrial production of nitric acid from ammonia. [13] This reaction is negligibly slow at low concentrations of NO2 characteristic of the ambient atmosphere, although it does proceed upon NO2 uptake to surfaces. Such surface reaction is thought to produce gaseous HNO2 (often written as HONO) in outdoor and indoor environments. [14]
NO2 is used to generate anhydrous metal nitrates from the oxides: [11]
Alkyl and metal iodides give the corresponding nitrates: [10]
NO2 is introduced into the environment by natural causes, including entry from the stratosphere, bacterial respiration, volcanos, and lightning. These sources make NO2 a trace gas in the atmosphere of Earth, where it plays a role in absorbing sunlight and regulating the chemistry of the troposphere, especially in determining ozone concentrations. [15]
NO2 is used as an intermediate in the manufacturing of nitric acid, as a nitrating agent in the manufacturing of chemical explosives, as a polymerization inhibitor for acrylates, as a flour bleaching agent, [16] : 223 and as a room temperature sterilization agent. [17] It is also used as an oxidizer in rocket fuel, for example in red fuming nitric acid; it was used in the Titan rockets, to launch Project Gemini, in the maneuvering thrusters of the Space Shuttle, and in uncrewed space probes sent to various planets. [18]
For the general public, the most prominent sources of NO2 are internal combustion engines, as combustion temperatures are high enough to thermally combine some of the nitrogen and oxygen in the air to form NO2. [8] Outdoors, NO2 can be a result of traffic from motor vehicles. [19]
Indoors, exposure arises from cigarette smoke, [20] and butane and kerosene heaters and stoves. [21]
Workers in industries where NO2 is used are also exposed and are at risk for occupational lung diseases, and NIOSH has set exposure limits and safety standards. [7] Workers in high voltage areas especially those with spark or plasma creation are at risk.[ citation needed ] Agricultural workers can be exposed to NO2 arising from grain decomposing in silos; chronic exposure can lead to lung damage in a condition called "silo-filler's disease". [22] [23]
NO2 diffuses into the epithelial lining fluid (ELF) of the respiratory epithelium and dissolves. There, it chemically reacts with antioxidant and lipid molecules in the ELF. The health effects of NO2 are caused by the reaction products or their metabolites, which are reactive nitrogen species and reactive oxygen species that can drive bronchoconstriction, inflammation, reduced immune response, and may have effects on the heart. [24]
Acute harm due to NO2 exposure is rare. 100–200 ppm can cause mild irritation of the nose and throat, 250–500 ppm can cause edema, leading to bronchitis or pneumonia, and levels above 1000 ppm can cause death due to asphyxiation from fluid in the lungs. There are often no symptoms at the time of exposure other than transient cough, fatigue or nausea, but over hours inflammation in the lungs causes edema. [25] [26]
For skin or eye exposure, the affected area is flushed with saline. For inhalation, oxygen is administered, bronchodilators may be administered, and if there are signs of methemoglobinemia, a condition that arises when nitrogen-based compounds affect the hemoglobin in red blood cells, methylene blue may be administered. [27] [28]
It is classified as an extremely hazardous substance in the United States as defined in Section 302 of the U.S. Emergency Planning and Community Right-to-Know Act (42 U.S.C. 11002), and it is subject to strict reporting requirements by facilities which produce, store, or use it in significant quantities. [29]
Exposure to low levels of NO2 over time can cause changes in lung function. [30] Chronic exposure to NO2 can cause respiratory effects including airway inflammation in healthy people and increased respiratory symptoms in people with asthma.
The effects of toxicity on health have been examined using questionnaires and in-person interviews in an effort to understand the relationship between NO2 and asthma. The influence of indoor air pollutants on health is important because the majority of people in the world spend more than 80% of their time indoors. [31] The amount of time spent indoors depends upon on several factors including geographical region, job activities, and gender among other variables. Additionally, because home insulation is improving, this can result in greater retention of indoor air pollutants, such as NO2. [31] With respect to geographic region, the prevalence of asthma has ranged from 2 to 20% with no clear indication as to what's driving the difference. [31] This may be a result of the "hygiene hypothesis" or "western lifestyle" that captures the notions of homes that are well insulated and with fewer inhabitants. [31] Another study examined the relationship between nitrogen exposure in the home and respiratory symptoms and found a statistically significant odds ratio of 2.23 (95% CI: 1.06, 4.72) among those with a medical diagnosis of asthma and gas stove exposure. [32]
A major source of indoor exposure to NO2 is the use of gas stoves for cooking or heating in homes. According to the 2000 census, over half of US households use gas stoves [33] and indoor exposure levels of NO2 are, on average, at least three times higher in homes with gas stoves compared to electric stoves with the highest levels being in multifamily homes. Exposure to NO2 is especially harmful for children with asthma. Research has shown that children with asthma who live in homes with gas stoves have greater risk of respiratory symptoms such as wheezing, cough and chest tightness. [32] [34] Additionally, gas stove use was associated with reduced lung function in girls with asthma, although this association was not found in boys. [35] Using ventilation when operating gas stoves may reduce the risk of respiratory symptoms in children with asthma.
In a cohort study with inner-city minority African American Baltimore children to determine if there was a relationship between NO2 and asthma for children aged 2 to 6 years old, with an existing medical diagnosis of asthma, and one asthma related visit, families of lower socioeconomic status were more likely to have gas stoves in their homes. The study concluded that higher levels of NO2 within a home were linked to a greater level of respiratory symptoms among the study population. This further exemplifies that NO
2 toxicity is dangerous for children. [36]
Interaction of NO2 and other NOx with water, oxygen and other chemicals in the atmosphere can form acid rain which harms sensitive ecosystems such as lakes and forests. [37] Elevated levels of NO
2 can also harm vegetation, decreasing growth, and reduce crop yields. [38]
Nitrogen is a chemical element; it has symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at seventh in total abundance in the Milky Way and the Solar System. At standard temperature and pressure, two atoms of the element bond to form N2, a colorless and odorless diatomic gas. N2 forms about 78% of Earth's atmosphere, making it the most abundant uncombined element in air. Because of the volatility of nitrogen compounds, nitrogen is relatively rare in the solid parts of the Earth.
Nitric acid is the inorganic compound with the formula HNO3. It is a highly corrosive mineral acid. The compound is colorless, but samples tend to acquire a yellow cast over time due to decomposition into oxides of nitrogen. Most commercially available nitric acid has a concentration of 68% in water. When the solution contains more than 86% HNO3, it is referred to as fuming nitric acid. Depending on the amount of nitrogen dioxide present, fuming nitric acid is further characterized as red fuming nitric acid at concentrations above 86%, or white fuming nitric acid at concentrations above 95%.
The nitronium ion, [NO2]+, is a cation. It is an onium ion because its nitrogen atom has +1 charge, similar to ammonium ion [NH4]+. It is created by the removal of an electron from the paramagnetic nitrogen dioxide molecule NO2, or the protonation of nitric acid HNO3.
An oxide is a chemical compound containing at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– ion with oxygen in the oxidation state of −2. Most of the Earth's crust consists of oxides. Even materials considered pure elements often develop an oxide coating. For example, aluminium foil develops a thin skin of Al2O3 that protects the foil from further oxidation.
Ozone is an inorganic molecule with the chemical formula O
3. It is a pale blue gas with a distinctively pungent smell. It is an allotrope of oxygen that is much less stable than the diatomic allotrope O
2, breaking down in the lower atmosphere to O
2 (dioxygen). Ozone is formed from dioxygen by the action of ultraviolet (UV) light and electrical discharges within the Earth's atmosphere. It is present in very low concentrations throughout the atmosphere, with its highest concentration high in the ozone layer of the stratosphere, which absorbs most of the Sun's ultraviolet (UV) radiation.
The Ostwald process is a chemical process used for making nitric acid (HNO3). Wilhelm Ostwald developed the process, and he patented it in 1902. The Ostwald process is a mainstay of the modern chemical industry, and it provides the main raw material for the most common type of fertilizer production. Historically and practically, the Ostwald process is closely associated with the Haber process, which provides the requisite raw material, ammonia (NH3).
An oxidizing agent is a substance in a redox chemical reaction that gains or "accepts"/"receives" an electron from a reducing agent. In other words, an oxidizer is any substance that oxidizes another substance. The oxidation state, which describes the degree of loss of electrons, of the oxidizer decreases while that of the reductant increases; this is expressed by saying that oxidizers "undergo reduction" and "are reduced" while reducers "undergo oxidation" and "are oxidized". Common oxidizing agents are oxygen, hydrogen peroxide, and the halogens.
Dinitrogen tetroxide, commonly referred to as nitrogen tetroxide (NTO), and occasionally (usually among ex-USSR/Russia rocket engineers) as amyl, is the chemical compound N2O4. It is a useful reagent in chemical synthesis. It forms an equilibrium mixture with nitrogen dioxide. Its molar mass is 92.011 g/mol.
Red fuming nitric acid (RFNA) is a storable oxidizer used as a rocket propellant. It consists of 84% nitric acid, 13% dinitrogen tetroxide and 1–2% water. The color of red fuming nitric acid is due to the dinitrogen tetroxide, which breaks down partially to form nitrogen dioxide. The nitrogen dioxide dissolves until the liquid is saturated, and produces toxic fumes with a suffocating odor. RFNA increases the flammability of combustible materials and is highly exothermic when reacting with water.
Nitric oxide is a colorless gas with the formula NO. It is one of the principal oxides of nitrogen. Nitric oxide is a free radical: it has an unpaired electron, which is sometimes denoted by a dot in its chemical formula. Nitric oxide is also a heteronuclear diatomic molecule, a class of molecules whose study spawned early modern theories of chemical bonding.
Nitrogen oxide may refer to a binary compound of oxygen and nitrogen, or a mixture of such compounds:
Nitrous acid is a weak and monoprotic acid known only in solution, in the gas phase, and in the form of nitrite salts. It was discovered by Carl Wilhelm Scheele, who called it "phlogisticated acid of niter". Nitrous acid is used to make diazonium salts from amines. The resulting diazonium salts are reagents in azo coupling reactions to give azo dyes.
Dinitrogen pentoxide is the chemical compound with the formula N2O5. It is one of the binary nitrogen oxides, a family of compounds that only contain nitrogen and oxygen. It exists as colourless crystals that sublime slightly above room temperature, yielding a colorless gas.
The lead chamber process was an industrial method used to produce sulfuric acid in large quantities. It has been largely supplanted by the contact process.
In atmospheric chemistry, NOx is shorthand for nitric oxide and nitrogen dioxide, the nitrogen oxides that are most relevant for air pollution. These gases contribute to the formation of smog and acid rain, as well as affecting tropospheric ozone.
The chemical element nitrogen is one of the most abundant elements in the universe and can form many compounds. It can take several oxidation states; but the most common oxidation states are -3 and +3. Nitrogen can form nitride and nitrate ions. It also forms a part of nitric acid and nitrate salts. Nitrogen compounds also have an important role in organic chemistry, as nitrogen is part of proteins, amino acids and adenosine triphosphate.
The Birkeland–Eyde process was one of the competing industrial processes in the beginning of nitrogen-based fertilizer production. It is a multi-step nitrogen fixation reaction that uses electrical arcs to react atmospheric nitrogen (N2) with oxygen (O2), ultimately producing nitric acid (HNO3) with water. The resultant nitric acid was then used as a source of nitrate (NO3−) in the reaction which may take place in the presence of water or another proton acceptor.
Reactive nitrogen species (RNS) are a family of antimicrobial molecules derived from nitric oxide (•NO) and superoxide (O2•−) produced via the enzymatic activity of inducible nitric oxide synthase 2 (NOS2) and NADPH oxidase respectively. NOS2 is expressed primarily in macrophages after induction by cytokines and microbial products, notably interferon-gamma (IFN-γ) and lipopolysaccharide (LPS).
Nitrogen dioxide poisoning is the illness resulting from the toxic effect of nitrogen dioxide. It usually occurs after the inhalation of the gas beyond the threshold limit value. Nitrogen dioxide is reddish-brown with a very harsh smell at high concentrations, at lower concentrations it is colorless but may still have a harsh odour. Nitrogen dioxide poisoning depends on the duration, frequency, and intensity of exposure.
A transition metal nitrate complex is a coordination compound containing one or more nitrate ligands. Such complexes are common starting reagents for the preparation of other compounds.